CN103436724B - Method for quickly preparing high-performance PbS(1-x)Sex based thermoelectric material - Google Patents

Method for quickly preparing high-performance PbS(1-x)Sex based thermoelectric material Download PDF

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CN103436724B
CN103436724B CN201310430713.7A CN201310430713A CN103436724B CN 103436724 B CN103436724 B CN 103436724B CN 201310430713 A CN201310430713 A CN 201310430713A CN 103436724 B CN103436724 B CN 103436724B
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powder
pbs
performance
base thermoelectricity
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CN103436724A (en
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唐新峰
张强
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Priority to US14/441,446 priority patent/US10500642B2/en
Priority to EP14767900.5A priority patent/EP2977129B1/en
Priority to JP2015540043A priority patent/JP6219399B2/en
Priority to PCT/CN2014/000287 priority patent/WO2014146485A1/en
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Priority to US16/667,110 priority patent/US10913115B2/en
Priority to US16/667,173 priority patent/US10913119B2/en
Priority to US16/667,128 priority patent/US10913116B2/en
Priority to US16/667,180 priority patent/US11433456B2/en
Priority to US16/667,143 priority patent/US10913117B2/en
Priority to US16/667,081 priority patent/US10913114B2/en
Priority to US16/667,158 priority patent/US10913118B2/en
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Abstract

The invention relates to a new method for quickly preparing a high-performance PbS(1-x)Sex based thermoelectric material. The new method comprises the following steps of: 1) weighing Pb powder, S powder and Se powder as raw materials according to the stoichiometric ratio of all the atoms in PbS(1-x+y)Se(x+z), wherein x is greater than or equal to 0 and less than 1.0, y is equal to 0.02 and z is equal to 0; and when x is equal to 1.0, y is equal to 0 and z is equal to 0.02; next, grinding the powdery raw materials and mixing evenly, and then pressing into blocks; 2) arousing the self-propagating reaction of the blocks obtained in the step 1), naturally cooling after the reaction is completed, thereby obtaining a single-phase PbS(1-x)Sex solid solution; 3) grinding the PbS(1-x)Sex solid solution into powder, performing discharge plasma activated sintering to obtain the high-performance PbS(1-x)Sex based thermoelectric material. The new method provided by the invention has the advantages of high reaction speed, simple process, high efficiency and energy conservation, good repeatability and the like; the whole preparation process can be completed in 0.5 hour.

Description

A kind of high-performance PbS of preparation fast 1-xse xthe method of base thermoelectricity material
Technical field
The invention belongs to technical field of new energy material preparation, be specifically related to a kind of high-performance PbS of preparation fast 1-xse xthe novel method of base thermoelectricity material.
Background technology
The efficient energy conversion material of development of new and technology, can alleviate the day by day exhaustion of destruction and the fossil energy day by day of physical environment.At present, a lot of scientific worker in the whole world, is finding its visual cognitive ability and exploitation thermoelectric generation technology---in reproducible new forms of energy switch technology.
The directly mutual conversion that thermoelectric generation technology can realize between electric energy and heat energy by the Seebeck effect of thermoelectric material and Peltier effect, it is as a kind of environmentally friendly Energy conversion technology at industrial exhaust heat and used heat, and there is important application prospect the recycling aspects such as automobile exhaust gas.Simultaneously it also has the advantages such as, noiselessness, good reliability little without drive disk assembly, volume.The efficiency of conversion of thermoelectric material is primarily of thermoelectric figure of merit zTdetermine, zT= a 2 s T/ k, wherein afor Seebeck coefficient, sfor specific conductivity, kfor thermal conductivity, tfor absolute temperature.
PbS 1-xse xthe thermoelectric material of matrix system, has good electrical property and lower thermal conductivity, thus has higher zTvalue.Meanwhile, it has raw material and contains the advantages such as abundant and cheap.
At present, PbS is prepared 1-xse xthe method of base thermoelectricity material mainly adopts scorification.But, scorification temperature required higher (﹥ 1100 DEG C), and the fusing point of element own is very low, Pb(327 DEG C), S(115 DEG C) and Se(221 DEG C), may cause the loss of element evaporation like this, simultaneously the required reaction times is longer, therefore, in energy-efficient, certain deficiency is had.Therefore, a kind of simple and fast, less energy consumption, reproducible synthetic method are for preparation PbS 1-xse xbase thermoelectricity material, seems extremely important.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of high-performance PbS of preparation fast 1-xse xthe method of base thermoelectricity material, speed of response is fast, technique is simple, reproducible, the PbS prepared 1-xse xbase compact block thermoelectric material thermoelectricity capability is excellent.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
A kind of high-performance PbS of preparation fast 1-xse xthe novel method of base thermoelectricity material, it comprises the following steps:
1) by PbS 1-x+yse x+zthe stoichiometric ratio of each atom takes Pb powder, S powder, Se powder as raw material, wherein when x be more than or equal to 0 be less than 1.0 time (0≤x ﹤ 1.0), y=0.02, z=0; As x=1.0, y=0, z=0.02, then that raw material powder ground and mixed is even, then that their ground and mixed is even, the powder mixed is pressed into block;
2) step 1) gained block is caused self-propagating reaction (SHS, Self-propagating High-temperature Synthesis) and reacted rear naturally cooling, single-phase PbS can be obtained 1-xse xcompound;
3) by above-mentioned products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, Plasma Activated Sintering), obtain high-performance PbS 1-xse xbase thermoelectricity material.
In such scheme, in described step 1), the quality purity of Pb powder, S powder and Se powder is all not less than 99.9%.
In such scheme, described step 2) in self-propagating reaction be that initiation reaction is heated to block end.
In such scheme, described step 2) in use air atmosphere or vacuum atmosphere or inert gas atmosphere in self-propagating reaction.
In such scheme, the process that described step 3) powder carries out discharge plasma activated sintering is: powder being loaded diameter is compacting in the graphite jig of 15mm, then sinter under vacuum is less than 10Pa and sintering pressure is 35MPa condition, 550 DEG C are warmed up to, sintering densification time 7min with the temperature rise rate of 100 DEG C/min.
Above-mentioned preparation method obtains high-performance PbS 1-xse xbase compact block thermoelectric material, at x=0 place, the thermoelectricity capability figure of merit zT0.5 is reached at 875K.
Based on foregoing, under the prerequisite not departing from basic fundamental thought of the present invention, according to ordinary technical knowledge and the means of this area, the amendment of various ways, replacement or change can also be had, as self-propagating reaction atmosphere can be changed to other rare gas element etc. do not reacted with Pb powder, S powder and Se powder to its content.
The present invention needs to provide necessary energy to bring out thermal chemical reaction to raw material, and form combustion wave, reaction after this just proceeds under the support of reacting institute's release of heat before, the PbS needed for reaction is formed after spreading and terminating 1-xse xbase thermoelectricity material powder.
With existing PbS 1-xse xpreparation method compares, and advantage of the present invention is:
The first, the present invention adopts SHS technology to prepare PbS first 1-xse xbase thermoelectricity material, has that speed of response is fast, equipment is simple, an advantage such as reproducible, energy-efficient and temperature rate is fast;
The second, the present invention can prepare PbS in 0.5h 1-xse xbase compact block thermoelectric material, and material cost is cheap.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of block after powder and PAS after SHS in embodiment 1.
Fig. 2 is Powder XRD pattern after SHS in embodiment 2.
Fig. 3 is the XRD figure spectrum of block after powder and PAS after SHS in embodiment 3.
Fig. 4 is Powder XRD pattern after SHS in embodiment 4.
Fig. 5 is Powder XRD pattern after SHS in embodiment 5.
The XRD figure that Fig. 6 (a) is block after powder after SHS and PAS is composed; Fig. 6 (b) is step 2) in after SHS powder SEM figure (from left to right amplify respectively 5.00 k doubly and 10.00 k doubly); Fig. 6 (c) is sintering block zero dimension thermoelectric figure of merit zTthe highest thermoelectric figure of merit of the material prepared with scorification zTtemperature variant graph of a relation.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
In following embodiment, the quality purity of Pb powder, S powder and Se powder is all not less than 99.9%.Self-propagating reaction (SHS) products therefrom " SHS " mark in Figure of description, discharge plasma activated sintering (PAS) products therefrom " PAS " mark.
embodiment 1
A kind of high-performance PbS of preparation fast 1-xse xthe novel method of base thermoelectricity material, it comprises the following steps:
1) by chemical formula PbSe (1+0.02)(i.e. PbS 1-x+yse x+zmiddle x=1.0, y=0, z=0.02) in, the stoichiometric ratio of each atom takes Pb powder, Se powder as raw material (note: Se excessive 2%, the i.e. value of z, to compensate Se volatilization loss in the reaction), total mass 4.5g, then by even for their ground and mixed, the powder mixed is pressed into the cylindrical block block (pressing process is: prior to 5MPa pressurize 5min, then in 8MPa pressurize 10min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS) and react rear naturally cooling;
3) by above-mentioned products therefrom grind into powder, powder is loaded compacting in the graphite jig of 15mm, then under vacuum is less than 10Pa and sintering pressure is 35MPa condition, discharge plasma activated sintering (PAS) is carried out, 550 DEG C are warmed up to the temperature rise rate of 100 DEG C/min, the sintering densification time is 7min, obtains PbSe compact block thermoelectric material.
As can be seen from Figure 1, self-propagating reaction (SHS) afterwards, discharge plasma activated sintering (PAS) afterwards products therefrom be single-phase PbSe compound.
embodiment 2
A kind of high-performance PbS of preparation fast 1-xse xthe novel method of base thermoelectricity material, it comprises the following steps:
1) by PbS (0.2+0.02)se 0.8(i.e. PbS 1-x+yse x+zmiddle x=0.8, y=0.02, z=0) in, the stoichiometric ratio of each atom takes Pb powder, S powder, Se powder as raw material (note: S excessive 2%, the i.e. value of y, to compensate S volatilization loss in the reaction), total mass 4.5g, then by even for their ground and mixed, the powder mixed is pressed into the cylindrical block block (pressing process is: prior to 5MPa pressurize 5min, then in 8MPa pressurize 10min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS) and react rear naturally cooling;
3) above-mentioned products therefrom grind into powder is carried out XRD test.
As can be seen from Figure 2, self-propagating reaction (SHS) afterwards products therefrom be single-phase PbS 0.2se 0.8sosoloid.
embodiment 3
A kind of high-performance PbS of preparation fast 1-xse xthe novel method of base thermoelectricity material, it comprises the following steps:
1) by PbS (0.4+0.02)se 0.6(i.e. PbS 1-x+yse x+zmiddle x=0.6, y=0.02, z=0) in, the stoichiometric ratio of each atom takes Pb powder, S powder, Se powder as raw material (note: S excessive 2%, to compensate S volatilization loss in the reaction), total mass 4.5g, then their ground and mixed is even, the powder mixed is pressed into the cylindrical block block (pressing process is: prior to 5MPa pressurize 5min, then in 8MPa pressurize 10min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS) and react rear naturally cooling;
3) by above-mentioned products therefrom grind into powder, powder is loaded compacting in the graphite jig of 15mm, then under vacuum is less than 10Pa and sintering pressure is 35MPa condition, discharge plasma activated sintering (PAS) is carried out, 550 DEG C are warmed up to the temperature rise rate of 100 DEG C/min, the sintering densification time is 7min, obtains PbSe compact block thermoelectric material.
As can be seen from Figure 3, self-propagating reaction (SHS) afterwards, discharge plasma activated sintering (PAS) afterwards products therefrom be single-phase PbS 0.4se 0.6sosoloid.
embodiment 4
A kind of high-performance PbS of preparation fast 1-xse xthe novel method of base thermoelectricity material, it comprises the following steps:
1) by PbS (0.6+0.02)se 0.4(i.e. PbS 1-x+yse x+zmiddle x=0.4, y=0.02, z=0) in, the stoichiometric ratio of each atom takes Pb powder, S powder, Se powder as raw material (note: S excessive 2%, to compensate S volatilization loss in the reaction), total mass 4.5g, then their ground and mixed is even, the powder mixed is pressed into the cylindrical block block (pressing process is: prior to 5MPa pressurize 5min, then in 8MPa pressurize 10min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS) and react rear naturally cooling;
3) above-mentioned products therefrom grind into powder is carried out XRD test.
As can be seen from Figure 4, self-propagating reaction (SHS) afterwards products therefrom be single-phase PbS 0.6se 0.4sosoloid.
embodiment 5
A kind of high-performance PbS of preparation fast 1-xse xthe novel method of base thermoelectricity material, it comprises the following steps:
1) by PbS (0.8+0.02)se 0.2(i.e. PbS 1-x+yse x+zmiddle x=0.2, y=0.02, z=0) in, the stoichiometric ratio of each atom takes Pb powder, S powder, Se powder as raw material, total mass 4.5g, then by even for their ground and mixed, the powder mixed is pressed into the cylindrical block block (pressing process is: prior to 5MPa pressurize 5min, then in 8MPa pressurize 10min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS) and react rear naturally cooling;
3) above-mentioned products therefrom grind into powder is carried out XRD test.
As can be seen from Figure 2, self-propagating reaction (SHS) afterwards products therefrom be single-phase PbS 0.8se 0.2sosoloid.
embodiment 6
A kind of high-performance PbS of preparation fast 1-xse xthe novel method of base thermoelectricity material, it comprises the following steps:
1) by PbS (1+0.02)(i.e. PbS 1-x+yse x+zmiddle x=1, y=0, z=0.02) in, the stoichiometric ratio of each atom takes Pb powder, S powder as raw material, total mass 4.5g, then by even for their ground and mixed, the powder mixed is pressed into the cylindrical block block (pressing process is: prior to 5MPa pressurize 5min, then in 8MPa pressurize 10min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS) and react rear naturally cooling;
3) by above-mentioned products therefrom grind into powder, powder is loaded compacting in the graphite jig of 15mm, then under vacuum is less than 10Pa and sintering pressure is 35MPa condition, discharge plasma activated sintering (PAS) is carried out, 550 DEG C are warmed up to the temperature rise rate of 100 DEG C/min, the sintering densification time is 7min, obtains PbS compact block thermoelectric material.
Fig. 6 (a) for self-propagating reaction (SHS) after product powder and discharge plasma activated sintering (PAS) afterwards block product XRD figure spectrum; Fig. 6 (b) is step 2) in after SHS powder SEM figure (from left to right amplify respectively 5.00 k doubly and 10.00 k doubly); Fig. 6 (c) is block zero dimension thermoelectric figure of merit after PAS zTthe highest thermoelectric figure of merit of the material prepared with comparative example scorification zTtemperature variant graph of a relation.
As can be seen from Figure 6, after SHS, products therefrom is single-phase PbS compound, and its powder grain size range is distributed more widely; After PAS, gained block is single-phase PbS compound, thermoelectric material prepared by this kind of method, and in the temperature range of more than 600K, the ratio of comparing has higher average zTvalue, when temperature is 875K, can reach meanwhile zT~ 0.57, compared with comparative example, increase rate is close to 100%.
comparative example
Scorification technique: Pb powder, S powder are as raw material, mix according to mol ratio 1:1, at the uniform velocity be raised to 1100 DEG C (time of at the uniform velocity heating up is 12h) from room temperature, and at 1100 DEG C of place's insulation 6h, then carry out PAS sintering, PAS technique is: vacuum is less than 10Pa, and sintering pressure is 35MPa, be warmed up to 550 DEG C with the temperature rise rate of 100 DEG C/min, the sintering densification time is 7min.

Claims (7)

1. prepare high-performance PbS fast for one kind 1-xse xthe method of base thermoelectricity material, is characterized in that it comprises the following steps:
1) by PbS 1-x+yse x+zthe stoichiometric ratio of each atom takes Pb powder, S powder and Se powder as raw material, and wherein the span of x, y, z is: 0≤x ﹤ 1.0, and y=0.02, and z=0; Or during x=1.0, and y=0, and z=0.02, then by powder stock ground and mixed evenly after be pressed into block;
2) step 1) gained block is caused self-propagating reaction, reacted rear naturally cooling, all can obtain single-phase PbS 1-xse xsosoloid;
3) by above-mentioned gained PbS 1-xse xsosoloid grind into powder, carries out discharge plasma activated sintering, obtains high-performance PbS 1-xse xbase thermoelectricity material.
2. one according to claim 1 prepares high-performance PbS fast 1-xse xthe method of base thermoelectricity material, is characterized in that the quality purity of Pb powder in described step 1), S powder and Se powder is all not less than 99.9%.
3. one according to claim 1 prepares high-performance PbS fast 1-xse xthe method of base thermoelectricity material, is characterized in that described step 1) pressing process is: the first step, pressurize 5min under 5MPa; Second step, pressurize 10min under 8MPa.
4. one according to claim 1 prepares high-performance PbS fast 1-xse xthe method of base thermoelectricity material, is characterized in that described step 2) in self-propagating reaction be that initiation reaction is heated to block end.
5. one according to claim 1 prepares high-performance PbS fast 1-xse xthe method of base thermoelectricity material, is characterized in that described step 2) in use air atmosphere or vacuum atmosphere or inert gas atmosphere in self-propagating reaction.
6. one according to claim 1 prepares high-performance PbS fast 1-xse xthe method of base thermoelectricity material, it is characterized in that the process that powder in described step 3) carries out discharge plasma activated sintering is: powder being loaded diameter is compacting in the graphite jig of 15mm, then sinter under vacuum is less than 10Pa and sintering pressure is 35MPa condition, 550 DEG C are warmed up to, sintering densification time 7min with the temperature rise rate of 100 DEG C/min.
7. described in claim 1, method obtains high-performance PbS 1-xse xbase thermoelectricity material.
CN201310430713.7A 2013-03-19 2013-09-22 Method for quickly preparing high-performance PbS(1-x)Sex based thermoelectric material Active CN103436724B (en)

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Application Number Priority Date Filing Date Title
CN201310430713.7A CN103436724B (en) 2013-09-22 2013-09-22 Method for quickly preparing high-performance PbS(1-x)Sex based thermoelectric material
US14/441,446 US10500642B2 (en) 2013-03-19 2014-03-17 Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof
EP14767900.5A EP2977129B1 (en) 2013-03-19 2014-03-17 Thermoelectric compound preparation based on self-propagating combustion synthesis new criterion
JP2015540043A JP6219399B2 (en) 2013-03-19 2014-03-17 Determination method of self-propagating combustion synthesis and preparation method of thermoelectric compounds based on the new criteria
PCT/CN2014/000287 WO2014146485A1 (en) 2013-03-19 2014-03-17 Thermoelectric compound preparation based on self-propagating combustion synthesis new criterion
US16/667,158 US10913118B2 (en) 2013-03-19 2019-10-29 Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof
US16/667,110 US10913115B2 (en) 2013-03-19 2019-10-29 Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof
US16/667,081 US10913114B2 (en) 2013-03-19 2019-10-29 Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof
US16/667,173 US10913119B2 (en) 2013-03-19 2019-10-29 Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof
US16/667,128 US10913116B2 (en) 2013-03-19 2019-10-29 Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof
US16/667,180 US11433456B2 (en) 2013-03-19 2019-10-29 Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof
US16/667,143 US10913117B2 (en) 2013-03-19 2019-10-29 Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof

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US10500642B2 (en) 2013-03-19 2019-12-10 Wuhan University Of Technology Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof
CN103934459B (en) * 2014-01-20 2016-05-11 武汉理工大学 A kind of supper-fast low cost is prepared the method for high-performance Half-Heusler block thermoelectric material
CN104946918A (en) * 2015-05-25 2015-09-30 武汉理工大学 New method for quickly preparing AgInSe2 based thermoelectric material
CN105152143B (en) * 2015-07-22 2018-08-07 武汉理工大学 A kind of Bi2SeO2The burning synthesis method and its combustion adjuvant of base thermoelectricity material
CN106711317B (en) * 2016-11-22 2019-06-11 同济大学 A kind of sulfur family leaded object thermoelectric material and preparation method thereof

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